EP4160772A1 - Lithium-ionen-sekundärbatterie, batteriemodul, batteriepack und elektrische vorrichtung - Google Patents

Lithium-ionen-sekundärbatterie, batteriemodul, batteriepack und elektrische vorrichtung Download PDF

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Publication number
EP4160772A1
EP4160772A1 EP21921632.2A EP21921632A EP4160772A1 EP 4160772 A1 EP4160772 A1 EP 4160772A1 EP 21921632 A EP21921632 A EP 21921632A EP 4160772 A1 EP4160772 A1 EP 4160772A1
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Prior art keywords
lithium
ion secondary
secondary battery
positive electrode
negative electrode
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French (fr)
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EP4160772A4 (de
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Cuiping Zhang
Changlong Han
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Contemporary Amperex Technology Hong Kong Ltd
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This application relates to the field of lithium-ion secondary batteries, and in particular, to a lithium-ion secondary battery having high energy density and high thermal stability, a battery module, a battery pack, and an electric apparatus.
  • lithium-ion secondary batteries have become the most popular energy storage system, and are currently widely used in battery electric vehicles, hybrid electric vehicles, smart power grids, and other fields.
  • a high-nickel ternary positive electrode material is undoubtedly the most direct way to increase the energy density.
  • an increase in an amount of nickel in a positive electrode active substance causes thermal stability of the positive electrode active substance to drop, making it easy to produce reactive oxygen, triggering oxygenation of an electrolyte, and producing more heat.
  • an external temperature is high (extreme weather in South China or Africa)
  • heat cannot be dissipated in time, leading to a sharp rise in a temperature of a cell, which further triggers decomposition of the electrolyte.
  • Such vicious cycle eventually leads to thermal runaway of the cell, to be specific, the sharp rise in the temperature of the cell, causing smoke, fire, or severe safety accidents.
  • An objective of this application is to provide a lithium-ion secondary battery, to resolve a problem of poor thermal stability of high-energy-density cells by using a high-nickel ternary positive electrode material.
  • a first aspect of this application provides a lithium-ion secondary battery including a positive electrode plate, a negative electrode plate, a separator, and an electrolyte, where the positive electrode plate includes a positive electrode current collector and a positive electrode material layer disposed on at least one surface of the positive electrode current collector, and the positive electrode material layer contains a positive electrode active substance, where
  • the electrolyte containing a specified amount of the compounds represented by formula (1), formula (2), and formula (3) is used in the lithium-ion secondary battery containing the high-nickel positive electrode active substance, so that the battery can have excellent high-temperature storage performance, a high thermal runaway temperature, and excellent low-temperature discharge power performance while obtaining high cell energy density.
  • W1% is in a range of 1%-15%, and optionally 3%-10%. In this way, conductivity of the electrolyte can be further improved, and an electrode plate material can be better infiltrated.
  • W2% is in a range of 1%-20%, and optionally 5%-15%. In this way, safety performance of the battery can be improved, with conductivity of the electrolyte guaranteed as well.
  • W3% is in a range of 5%-20%, and optionally 5%-16%. In this way, thermal stability of the electrolyte can be better improved while avoiding corrosion of an aluminum foil.
  • R 1 to R 6 in formula (2) are each independently selected from halogen and a C1-C6 alkoxy group; and optionally R 1 to R 5 are all fluorine atoms and R 6 is a C1-C6 alkoxy group. A further selection of a substituent group can further improve safety performance of the cell.
  • the compound represented by formula (3) is lithium bis(fluorosulfonyl)imide.
  • a selection of the lithium bis(fluorosulfonyl)imide helps improve energy density of the cell and increase conductivity of the electrolyte.
  • the lithium-ion secondary battery satisfies at least one of the following conditions (a) and (b):
  • thermal stability and flame retardancy of the electrolyte can be improved, thereby significantly improving safety performance of the cell.
  • a selection of a value of x helps obtain a battery with stability and high energy density.
  • a total concentration of lithium salts in the electrolyte is 0.8M-1.5M, and optionally 0.8M-1.2M. A selection of the total concentration of the lithium salts helps improve power performance and safety of the cell.
  • the negative electrode plate includes a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, the negative electrode material layer contains a negative electrode active substance, and the negative electrode active substance contains graphite with OI ⁇ 8 whose percentage by weight is ⁇ 20% based on a total weight of the negative electrode active substance; and optionally, the percentage by weight of the graphite with OI ⁇ 8 is 10%-20% based on the total weight of the negative electrode active substance.
  • a combination of the specified amount of highly expanded graphite with OI ⁇ 8, the electrolyte, and the positive electrode active substance can significantly improve cycling performance, storage performance, and rate performance of the cell.
  • a second aspect of this application provides a battery module, including the lithium-ion secondary battery in the first aspect of this application.
  • a third aspect of this application provides a battery pack, including the battery module in the second aspect of this application.
  • a fourth aspect of this application provides an electric apparatus, including more than one of the lithium-ion secondary battery in the first aspect of this application, the battery module in the second aspect of this application, or the battery pack in the third aspect of this application.
  • any lower limit may be combined with any upper limit to form an unspecified range, and any lower limit may be combined with another lower limit to form an unspecified range, and likewise, any upper limit may be combined with any other upper limit to form an unspecified range.
  • each individually disclosed point or single numerical value as a lower limit or an upper limit, may be combined with any other point or single numerical value or combined with another lower limit or upper limit to form an unspecified range.
  • the most common method used to increase energy density of cells of lithium-ion secondary batteries is to increase an amount of nickel in a positive electrode material.
  • a large amount of LiOH and Li 2 CO 3 is usually present on a surface of a high-nickel ternary positive electrode active substance, and these substances are alkaline to some degree.
  • a conventional electrolyte using a LiPF 6 -carbonate solvent system decomposes at a high temperature, producing HF.
  • the HF produced reacts with LiOH and Li 2 CO 3 , destroying a positive electrode interface.
  • the electrolyte is constantly oxidized at the positive electrode interface, and active lithium is consumed, leading to a drop in cycling performance.
  • this side reaction of oxidation is further intensified due to a high potential of a positive electrode.
  • a decomposition product of the electrolyte deposits at cathode and anode interfaces, blocking migration of lithium ions, increasing a DCR, and reducing low-temperature discharge power.
  • much heat is produced in a battery charging and discharging process, which may ultimately pose safety problems.
  • a lithium-ion secondary battery includes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte.
  • active ions are intercalated and deintercalated between the positive electrode plate and the negative electrode plate.
  • the separator is disposed between the positive electrode plate and the negative electrode plate to provide separation.
  • the electrolyte is disposed between the positive electrode plate and the negative electrode plate to conduct ions.
  • a lithium-ion secondary battery in a first aspect of this application includes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte, where the positive electrode plate includes a positive electrode current collector and a positive electrode material layer disposed on at least one surface of the positive electrode current collector, and the positive electrode material layer contains a positive electrode active substance, where
  • the electrolyte containing a specified amount of the compounds represented by formula (1), formula (2), and formula (3) is used in the lithium-ion secondary battery containing the high-nickel positive electrode active substance, so that the battery can have excellent high-temperature storage performance, a high thermal runaway temperature, and excellent low-temperature discharge power performance while obtaining high cell energy density.
  • a value of W3/W2 is less than 1, not only viscosity of the electrolyte increases significantly, but also an amount of a dissociable lithium salt in the electrolyte is low. As a result, conductivity of the electrolyte decreases significantly, heavily affecting service life, rate performance, power, and other performance of the cell.
  • the ratio of the number of halogen atoms to the number of P atoms in the compound represented by formula (2) it can be ensured that the compound decomposes and absorbs heat at a thermal runaway temperature of the cell (the temperature is ⁇ 100°C), produces phosphate that deposits on surfaces of the electrode plates, prevents the electrolyte from coming into contact with the electrode plates, and relieves the thermal runaway, and sufficient halogen free radicals are produced to effectively trap hydrogen free radicals and oxygen free radicals, thereby significantly improving safety performance of the cell.
  • the ratio of the number of halogen atoms to the number of P atoms is less than 1:3, although the compound decomposes and produces solid phosphate, it is difficult to eliminate hydrogen free radicals and oxygen free radicals produced by decomposition of the electrolyte. Therefore, a chain reaction of thermal decomposition of the electrolyte is not terminated, and it is difficult to significantly improve safety of the cell.
  • the ratio of the number of halogen atoms to the number of P atoms is greater than 2: 1, phosphate produced by the composition of the compound is too little to fully cover a positive electrode interface and a negative electrode interface, and therefore cannot prevent a side reaction of the electrolyte at the positive electrode interface and the negative electrode interface.
  • W1% is in a range of 1%-15%, and optionally 3%-10%.
  • a selection of the percentage by weight of the compound represented by formula (1) can further improve conductivity of the electrolyte, and an electrode plate material can be better infiltrated.
  • W2% is in a range of 1%-20%, and optionally 5%-15%.
  • a selection of the percentage by weight of the compound represented by formula (2) can improve safety performance of the battery, with conductivity of the electrolyte guaranteed as well.
  • W3% is in a range of 5%-20%, and optionally 5%-16%.
  • a selection of the percentage by weight of the compound represented by formula (3) can better improve thermal stability of the electrolyte, while avoiding corrosion of an aluminum foil.
  • R 1 to R 6 in formula (2) are each independently selected from halogen and a C1-C6 alkoxy group; and optionally R 1 to R 5 are all fluorine atoms and R 6 is a C1-C6 alkoxy group.
  • Phosphonitrile represented by formula (2) may decompose at a high temperature, and phosphorus-containing and fluorine-containing free radical groups produced therefrom can trap hydroxide radicals produced by decomposition of a solvent in the electrolyte, which terminates a chain reaction of the solvent, improving safety performance.
  • a further selection of a substituent group of a phosphonitrile structure can further improve safety performance of the cell.
  • the compound represented by formula (3) is lithium bis(fluorosulfonyl)imide.
  • bis(fluorosulfonyl)imide has a minimum molecular weight, with a minimum mass in a case of an equal quantity, which reduces a mass of the cell and increases energy density of the cell to some degrees.
  • bis(fluorosulfonyl)imide is easier to dissociate lithium ions, thereby helping increase conductivity of the electrolyte.
  • the lithium-ion secondary battery satisfies at least one of the following conditions (a) and (b):
  • 0.65 ⁇ x ⁇ 0.9, and optionally x 0.8.
  • x is greater than 0.9, a structure of the positive electrode tends to be unstable, leading to serious oxidation of the electrolyte in a full charge state of the battery.
  • x is less than 0.65, the positive electrode is stable.
  • a gram capacity of the material is too low to meet a requirement of high energy density for the battery.
  • a total concentration of lithium salts in the electrolyte is 0.8M-1.5M, and optionally 0.8M-1.2M.
  • the inventors find that affected by the concentration of the lithium salts, conductivity of the electrolyte presents a parabolic pattern. If the concentration of the lithium salts is excessively high, viscosity of the electrolyte may increase sharply and the number of lithium ions dissociated increases slowly. Therefore, the conductivity of the electrolyte also decreases, which deteriorates power performance of the cell. In addition, the concentration of the lithium salts in the electrolyte further directly affects safety performance of the cell.
  • the negative electrode plate includes a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, the negative electrode material layer contains a negative electrode active substance, and the negative electrode active substance contains graphite with OI ⁇ 8 whose percentage by weight is ⁇ 20% based on a total weight of the negative electrode active substance; and optionally, the percentage by weight of the graphite with OI ⁇ 8 is 10%-20% based on the total weight of the negative electrode active substance.
  • a value of the OI has a meaning commonly understood in the art, referring to a degree of orientation.
  • high-capacity graphite for example, graphite with OI ⁇ 8
  • a high-nickel ternary positive electrode material to achieve high energy density.
  • lithium ions are easy to intercalate into the graphite during charging, resulting in expansion of a graphite electrode plate to some degrees.
  • the high-capacity graphite usually has a high degree of expansion.
  • the highly expanded graphite expands during a life cycle thereof and extrudes the electrolyte, leading to lithium precipitation at an anode, an increase in a thickness of the electrode plate, and deterioration of performance of the cell.
  • a combination of the highly expanded graphite with OI ⁇ 8 whose percentage by weight is ⁇ 20%, the electrolyte, and the positive electrode active substance can improve cycling performance, storage performance, and rate performance of the cell significantly.
  • the following describes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte of a battery separately.
  • the electrolyte is disposed between the positive electrode plate and the negative electrode plate to conduct ions.
  • the electrolyte includes an electrolytic salt and a solvent.
  • the electrolytic salt may be a common electrolytic salt in a lithium-ion secondary battery, for example, a lithium salt, including the lithium salt represented by the foregoing formula (3).
  • the electrolytic salt may be selected from more than one of LiPF 6 (lithium hexafluorophosphate), LiBF 4 (lithium tetrafluoroborate), LiAsF 6 (lithium hexafluoroarsenate), LiFSI (lithium bis(fluorosulfonyl)imide), LiTFSI (lithium bis-trifluoromethanesulfonimide), LiTFS (lithium trifluoromethanesulfonat), LiDFOB (lithium difluorooxalatoborate), LiPO 2 F 2 (lithium difluorophosphate), LiDFOP (lithium bis(oxyalyl)difluorophosphate), LiSO 3 F (lithium fluorosulfonate), difluorodioxalate Li 2 F(
  • the solvent is not particularly limited in type, and may be selected based on actual needs.
  • the solvent is a non-aqueous solvent.
  • the solvent may include one or more of linear carbonate, cyclic carbonate, and carboxylate.
  • the solvent may be further selected from more than one of ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methylmethyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl
  • EC ethylene
  • the solvent may be selected from one or more of diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethylene carbonate, propylene carbonate, butenyl carbonate, ethyl propyl carbonate, 1,4-butyrolactone, methyl formate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl propionate, and tetrahydrofuran, thereby providing a stable electrochemical environment for high-nickel lithium-ion batteries with a voltage of 4 V and above.
  • a mass percentage of the non-aqueous solvent in the electrolyte is 65%-85%.
  • the electrolyte further optionally includes other additives.
  • the additives may include a negative electrode film-forming additive, or may include a positive electrode film-forming additive, or may include an additive that can improve some performance of a battery, for example, an additive for improving over-charge performance of the battery, an additive for improving high-temperature performance of the battery, and an additive for improving low-temperature performance of the battery.
  • the additives are selected from at least one of cyclic carbonate compound containing unsaturated bonds, cyclic carbonate compound substituted by halogen, sulfate compound, sulfite compound, sultone compound, disulfonic compound, nitrile compound, aromatic compound, isocyanate compound, phosphonitrile compound, cyclic anhydride compound, phosphite ester compound, phosphate ester compound, borate compound, and carboxylic ester compound.
  • the positive electrode plate includes a positive electrode current collector and a positive electrode material layer disposed on at least one surface of the positive electrode current collector, and the positive electrode material layer includes a positive electrode active substance and carbon.
  • the positive electrode current collector has two opposite surfaces in a thickness direction thereof, and the positive electrode material layer is disposed on either or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil an aluminum foil may be used.
  • the composite current collector may include a polymer material matrix and a metal layer formed on at least one surface of the polymer material matrix.
  • the composite current collector may be formed by forming a metal material (for example, aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, or the like) on the polymer material matrix (for example, matrices of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE)).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active substance may further include one or more of lithium transition metal oxide, olivine-structured lithium-containing phosphate, and modified compounds thereof.
  • a percentage by weight of the LiNi x Co y N z M 1-x-y-z O 2 in a total weight of the positive electrode active substance is 60%-100%, and optionally 80%-100%.
  • Examples of the olivine-structured lithium-containing phosphate may include, but are not limited to, one or more of lithium iron phosphate, composite materials of lithium iron phosphate and carbon, lithium manganese phosphate, composite materials of lithium manganese phosphate and carbon, lithium manganese iron phosphate, composite materials of lithium manganese iron phosphate and carbon, and modified compounds thereof. These materials are all commercially available.
  • a surface of the positive electrode active substance may be coated with carbon.
  • the positive electrode material layer optionally includes a conductive agent.
  • the conductive agent is not limited to a specific type, and may be selected by persons skilled in the art based on actual needs.
  • the conductive agent used in the positive electrode material layer may be selected from more than one of Super P, superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofiber.
  • the positive electrode material layer further optionally includes a binder.
  • the binder may be one or more of styrene-butadiene rubber (SBR), water-based acrylic resin (water-based acrylic resin), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).
  • SBR styrene-butadiene rubber
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • EVA ethylene-vinyl acetate copolymer
  • PAA polyacrylic acid
  • CMC carboxymethyl cellulose
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • the positive electrode plate in this application may be prepared by using the method known in the art.
  • the positive electrode active substance, the conductive agent, and the binder may be dispersed in a solvent (for example, N-methylpyrrolidone (NMP)) to form a uniform positive electrode slurry, and the positive electrode slurry is applied on a positive electrode current collector, and processes such as drying and cold pressing are performed to obtain the positive electrode plate.
  • NMP N-methylpyrrolidone
  • the negative electrode plate includes a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, and the negative electrode material layer includes a negative electrode active substance.
  • the negative electrode current collector has two opposite surfaces in a thickness direction thereof, and the negative electrode material layer is disposed on either or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • a metal foil a copper foil may be used.
  • the composite current collector may include a polymer material matrix and a metal layer formed on at least one surface of the polymer material matrix.
  • the composite current collector may be formed by forming a metal material (for example, copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, or the like) on the polymer material matrix (for example, matrices of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE)).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode material layer usually includes a negative electrode active substance, an optional binder, an optional conductive agent, and other optional additives, and is usually formed by being coated with a negative electrode slurry and dried.
  • the negative electrode slurry is usually obtained by dispersing the negative electrode active substance and the optional conductive agent, the optional binder, and the like in a solvent and stirring them to a uniform mixture.
  • the solvent may be N-methylpyrrolidone (NMP) or deionized water.
  • the negative electrode active substance is not limited.
  • An active substance known in the art that can be used as the negative electrode of the lithium-ion secondary battery may be used, and persons skilled in the art may select an active substance based on actual needs.
  • the negative electrode active substance may be selected from one or more of natural graphite, artificial graphite, mesocarbon microbeads (MCMB for short), hard carbon, soft carbon, silicon, a silicon-carbon composite, a Li-Sn alloy, a Li-Sn-O alloy, Sn, SnO, SnO 2 , spinel-structure lithiated TiO 2 -Li 4 Ti 5 O 12 , and a Li-Al alloy.
  • the conductive agent may be selected from more than one of Super P, superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofiber.
  • the binder may be selected from more than one of styrene butadiene rubber (SBR), polyacrylic acid (PAA), polyacrylic acid sodium (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
  • SBR styrene butadiene rubber
  • PAA polyacrylic acid
  • PAAS polyacrylic acid sodium
  • PAM polyacrylamide
  • PVA polyvinyl alcohol
  • SA sodium alginate
  • PMAA polymethacrylic acid
  • CMCS carboxymethyl chitosan
  • the other optional additives are, for example, a thickener (for example, sodium carboxymethyl cellulose (CMC-Na)).
  • a thickener for example, sodium carboxymethyl cellulose (CMC-Na)
  • Lithium-ion secondary batteries using an electrolyte further include a separator.
  • the separator is disposed between the positive electrode plate and the negative electrode plate to provide separation.
  • the separator is not limited to any specific type in this application, and may be any commonly known porous separator with good chemical stability and mechanical stability.
  • a material of the separator may be selected from more than one of glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.
  • the separator may be a single-layer film or a multi-layer composite film, and is not specifically limited. When the separator is a multi-layer composite film, all layers may be made of same or different materials, which is not particularly limited.
  • the positive electrode plate, the negative electrode plate, and the separator may be made into an electrode assembly through winding or lamination.
  • the lithium-ion secondary battery may include an outer package.
  • the outer package may be used for packaging the electrode assembly and the electrolyte.
  • an outer package of the lithium-ion secondary battery may be a hard shell, for example, a hard plastic shell, an aluminum shell, or a steel shell.
  • the outer package of the lithium-ion secondary battery may alternatively be a soft pack, for example, a soft pouch.
  • a material of the soft pack may be plastic.
  • polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS) may be listed.
  • FIG. 1 shows a lithium-ion secondary battery 5 of a square structure as an example.
  • the outer package may include a housing 51 and a cover plate 53.
  • the housing 51 may include a base plate and a side plate connected onto the base plate, and the base plate and the side plate enclose an accommodating cavity.
  • the housing 51 has an opening communicating with the accommodating cavity, and the cover plate 53 can cover the opening to close the accommodating cavity.
  • the positive electrode plate, the negative electrode plate, and the separator may be made into an electrode assembly 52 through winding or lamination.
  • the electrode assembly 52 is packaged in the accommodating cavity.
  • the electrolyte infiltrates the electrode assembly 52.
  • lithium-ion secondary batteries may be assembled into a battery module, and the battery module may include one or more lithium-ion secondary batteries.
  • a specific quantity may be chosen by persons skilled in the art based on use and capacity of the battery module.
  • FIG. 3 shows a battery module 4 as an example.
  • a plurality of lithium-ion secondary batteries 5 may be sequentially arranged in a length direction of the battery module 4.
  • the plurality of lithium-ion secondary batteries may alternatively be arranged in any other manner.
  • the plurality of lithium-ion secondary batteries 5 may be fixed by using fasteners.
  • the battery module 4 may further include a housing with an accommodating space, and the plurality of lithium-ion secondary batteries 5 are accommodated in the accommodating space.
  • the battery module may be further assembled into a battery pack, and a quantity of battery modules included in the battery pack may be chosen by persons skilled in the art based on use and capacity of the battery pack.
  • FIG. 4 and FIG. 5 show a battery pack 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 arranged in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can cover the lower box body 3 to form an enclosed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 may be arranged in the battery box in any manner.
  • this application further provides an apparatus.
  • the apparatus includes more than one of the lithium-ion secondary battery, the battery module, or the battery pack provided in this application.
  • the lithium-ion secondary battery, the battery module, or the battery pack may be used as a power source of the apparatus or an energy storage unit of the apparatus.
  • the apparatus may be, but is not limited to, a mobile device (for example, a mobile phone or a laptop computer), an electric vehicle (for example, a battery electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf vehicle, or an electric truck), an electric train, a ship, a satellite, an energy storage system, and the like.
  • a lithium-ion secondary battery, a battery module, or a battery pack may be selected for the apparatus according to requirements for using the apparatus.
  • FIG. 6 shows an apparatus as an example.
  • the apparatus is a battery electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, or the like.
  • a battery pack or a battery module may be used.
  • the apparatus may be a mobile phone, a tablet computer, a laptop computer, or the like.
  • Such apparatus is generally required to be light and thin, and may use a lithium-ion secondary battery as a power source.
  • a positive electrode active substance LiNi 0.8 Co 0.1 Mn 0.1 O 2 , a conductive agent Super P, and a binder polyvinylidene fluoride (PVDF) were added to N-methylpyrrolidone (NMP) at a mass ratio of 8:1:1 to prepare a positive electrode slurry.
  • NMP N-methylpyrrolidone
  • a percentage by weight of solids in the positive electrode slurry was 50%.
  • the positive electrode slurry was applied on a current collector aluminum foil (a mass of the positive electrode active material applied on the aluminum foil was 0.14 mg/mm 2 ), which was dried at 85°C and cold pressed, followed by trimming, cutting, slitting, and drying under a vacuum condition at 85°C for 4 h, to prepare a positive electrode plate.
  • a negative electrode active material graphite (a mass percentage of graphite with OI ⁇ 8 in total graphite was 10%), a conductive agent Super P, a thickener CMC, and a binder butadiene styrene rubber (SBR) were mixed uniformly in deionized water at a mass ratio of 80:15:3:2 to prepare a negative electrode slurry. A percentage by weight of solids in the negative electrode slurry was 30%.
  • the negative electrode slurry was applied on a current collector copper foil (a mass of the negative electrode active material applied on the copper foil was 0.08 mg/mm 2 ), which was dried at 85°C and cold pressed, followed by trimming, cutting, slitting, and drying under a vacuum condition at 120°C for 12 h, to prepare a negative electrode plate.
  • a polypropylene film (PE) with a thickness of 16 ⁇ m was used as a separator.
  • the positive electrode plate, the separator, and the negative electrode plate prepared were stacked in order, so that the separator was sandwiched between the positive electrode plate and the negative electrode plate for separation, and winding was performed to obtain a bare cell. Tabs were welded and the bare cell was placed in an outer package.
  • the prepared electrolyte was injected to the dried cell, followed by packaging, standing, formation, and shaping, to complete preparation of a lithium-ion secondary battery.
  • the battery had a thickness of 4.0 mm, a width of 60 mm, and a length of 140 mm.
  • a lithium-ion battery was charged to 4.2 V at a constant current of 1C, then charged to 0.05C at a constant voltage of 4.2 V, and then discharged to 2.8 V at 0.5C to obtain a discharge capacity D0.
  • the battery was stored in a 60°C thermostat and taken out after 30 days. After being cooled down to a room temperature, the battery was discharged to 2.8 V at a constant current of 1C, left standing for 5 minutes, charged to 4.2 V at a constant current of 1C, then charged to a current of 0.05C at a constant voltage of 4.2 V, and then discharged to 2.8 V at 0.5C.
  • a discharge capacity was D1
  • a reversible capacity retention rate of the battery after high-temperature storage was equal to D1/D0 ⁇ 100%.
  • a lithium-ion battery was charged to 4.2 V at a constant current of 1C, then charged to a current of 0.05C at a constant voltage of 4.2 V
  • a temperature sensing cable was attached to a central position on a surface of the cell. The battery was then placed in a heating oven that was heated up at a temperature rise rate of 10°C/min, and the oven was maintained at a temperature for 30 min every 10°C rise in temperature. In a case that a temperature sensed by the temperature sensing cable instantaneously and dramatically rose to a temperature far higher than that of the heating oven, it could be deemed that the cell experienced thermal runaway. The temperature of the heating oven when the battery experienced thermal runaway was recorded.
  • a lithium-ion battery was charged to 4.2 V at a constant current of 1C, then charged to a current of 0.05C at a constant voltage of 4.2 V, and then discharged for 30 minutes at 1C.
  • Tests were performed in a manner the same as those of Example 1-1, except that W1, W2, and W3 were changed, as shown in Table 1.
  • Tests were performed in a manner the same as those of Example 1-1, except that no fluorobenzene, ethoxy(pentafluoro)cyclotriphosphazene, or lithium bis(fluorosulfonyl)imide was used.
  • Tests were performed in a manner the same as those of Example 1-1, except that W1, W2, and W3 were changed.
  • Tests were performed in a manner the same as those of Example 1-1, except that types of positive electrode active substances were changed and W1, W2, and W3 were changed.
  • Example 3 Percentages by weight of substances in positive electrode active substances and electrolytes of Example 3-1 to Example 3-6 and performance test results of batteries are shown in Table 3.
  • Table 3 Example number Positive electrode active substance W1% W2% W3% W3/W2 W1/W2 Reversible capacity retention rate after high-temperature storage Thermal runaway temperature (°C) DCR (mOhm) 3-1 LiNi 0.5 Co 0.2 Mn 0.3 O 2 5% 5% 16% 3.2 1 99.0% 210 120 3-2 LiNi 0.5 Co 0.2 Mn 0.3 O 2 5% 6.25% 1.25 1 98.8% 220 100 3-3 LiNi 0.5 Co 0.2 Mn 0.3 O 2 5% 8% 16% 2 0.63 98.6% 215 127 3-4 LiNi 0.4 Co 0.2 Mn 0.4 O 2 4% 4% 16% 4 1 99.3% 250 115 3-5 LiNi 0.4 Co 0.2 Mn 0.4 O 2 4% 4% 4% 1 1 99.0% 265 128 3-6 LiNi 0.4 Co 0.2
  • Tests were performed in a manner the same as those of Example 1-1, except that trifluoromethylbenzene was used as the compound represented by formula (1), methoxy pentafluorocyclotriphosphazene was used as the compound represented by formula (2), lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide was used as the compound represented by formula (3), and values of W1, W2 and W3 shown in Table 4 were used.
  • the compound represented by formula (1) was not used in Comparative Example 5, and therefore low-temperature discharge power performance was poor.
  • the compound represented by formula (2) was not included in Comparative Example 6, and therefore a thermal runaway temperature of a cell was low.
  • the compound represented by formula (3) was not included in Comparative Example 7, and therefore a thermal runaway temperature of a cell was low, conductivity of an electrolyte was low, and low-temperature discharge power performance of the cell was poor.

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